Effects of iron oxide on crystallization behavior and spatial distribution of spinel in stainless steel slag

Chromium plays a vital role in stainless steel due to its ability to improve the corrosion resistance of the latter.However,the re-lease of chromium from stainless steel slag(SSS)during SSS stockpiling causes detrimental environmental issues.To prevent chromium pollution,the effects of iron oxide on crystallization behavior and spatial distribution of spinel were investigated in this work.The results revealed that FeO was more conducive to the growth of spinels compared with Fe2O3 and Fe3O4.Spinels were found to be mainly distrib-uted at the top and bottom of slag.The amount of spinel phase at the bottom decreased with the increasing FeO content,while that at the top increased.The average particle size of spinel in the slag with 18wt%FeO content was 12.8μm.Meanwhile,no notable structural changes were observed with a further increase in FeO content.In other words,the spatial distribution of spinel changed when the content of iron oxide varied in the range of 8wt%to 18wt%.Finally,less spinel was found at the bottom of slag with a FeO content of 23wt%.

Properties of Steel Slag and Stainless Steel Slag as Cement Replacement Materials:A Comparative Study

To enhance the understanding about the utilization of steel slags as a cementitious material, we comparatively studied the chemical, mineralogical and morphological properties of two types of steel slag; basicoxygen-furnace carbon slag(BOF C) and electric-arc-furnace stainless steel slag(EAF S). Moreover, we studied the standard consistency, setting time and the effect of the slag replacement ratios on the fluidity and compressive strength of blended cement mortar. The experimental results showed that BOF C had higher alkalinity, higher pH value and more hydraulic phases than EAF S. Both types of slag showed water reduction effect due to its high fineness. Neat BOF C paste showed flash set and acceleration in the initial setting time of blended cement especially at high slag proportions. However, EAF S prolonged the setting time of blended cement even at low slag proportions. The pH values for blended cement contained 50% BOF C or EAF S were lower than those of pure cement paste. Despite of slag type, compressive strength gradually decreased with increasing slags content. The strength of BOF C mortar was higher than that of EAF S mortar with the same replacement ratio for the same age. Slag activity index demonstrated that BOF C and EAF S conformed to the Chinese National Standard(GB/T 20491-2006) requirements for steel slag as grade one and grade two, respectively.

Challenges in the use of stainless steel slag

Stainless steel melting shops of Outokumpu Group are located in Finland,Sweden and England(UK). In all of the countries the European Union legislation is the same,but in practice the plants face different technical,economical and administrative challenges in developing sustainable treatments and use of by-products. Due to availability of good natural construction materials,the use of slag and other industrial by-products has been quite small in Northern Europe.Blast furnace slag has been completely utilized,while slag from stainless steel processes has earlier been regarded as waste.Steering of the metallurgical melt phase,slag cooling,treatment and metal recovery processes are the main technical challenges for increasing the sustainable use of stainless steel slag. Moreover,product properties have to fulfill standards and customer requirements.Dry or water-cooled EAF slag aggregates are typically used in road construction.Outokumpu has developed light mineral slag aggregates which are cooled in rapid water process.During this process,a specific structure and mineralogy is formed in the slag and leaching from the material decreases.In many regulatory discussions,it seems that there is not enough relevant scientific data from harmful compounds.Limit values are based only on laboratory tests and model estimations,not on the material use itself or real nature.A risk-based approach is needed when environmental acceptance is not clear.Limit values based on content are not applicable because environmental or health risks depend on the release or leaching of substances from the material.This is the case especially with metals.

Growth and aggregation control of spinel by shear-force-based melting modification of stainless steel slag

To improve the efficiency of melting modification for stainless steel(SS) slag, a shear force was introduced in this work and its effects on the spinel and silicate melt were experimentally investigated. The results indicated that the use of shear force changed the nucleation and growth behaviors of spinel and that the effects of shear force varied with its intensity. The aggregation behavior of spinel under different shear-force conditions was studied, revealing that large spinel clusters could be formed when the stirring speed was controlled. However, no notable change in the melt structure of the silicate was detected in this study. The optimal stirring speed for the melting modification treatment was 50 r·min^(-1), which substantially promoted spinel growth and aggregation, resulting in modified SS slag with excellent chromium sequestration capability.

Effect of Al2O3 modification on enrichment and stabilization of chromium in stainless steel slag

Spinel phase is considered to be the optimal phase for stabilization of chromium in stainless steel slag.In order to restrain chromium leaching from slag for the effective environmental protection,Al2O3 was utilized for the modification treatment,and the effects on the enrichment and stabilization of chromium were investigated. The mineral phases and the existence state of chromium in slag with various Al2O3 contents at different basicities（ w（CaO）/w（SiO2） were analyzed by scanning electron microscopy-energy dispersive spectroscopy（ SEM-EDS） and X-ray diffraction（ XRD）. The results showed that chromium mainly existed in the glass and spinel phases at basicity of 1. 0 and 1. 5. As the slag basicity increased to 2. 0,chromium was also found in periclase phase. Al2O3 in the stainless steel slag reacted with MgO and Cr2O3,which could generate the Al-rich Mg（CrxAl（1- x））2O4 solid solution. Moreover,the addition of Al2O3 was favorable to reduce the solubility of chromium oxide in liquid phase and suppress the precipitation of periclase phase. The experimental results demonstrated that Al2O3 modification has a positive influence on the enrichment and the stabilization of chromium in the stainless steel slag.

Crystallization mechanism of glass-ceramics prepared from stainless steel slag

Glass-ceramics have been prepared by using stainless steel slag, fly ash and coal fly ash that were figobtained from industrial solid waste. The crystallization behavior and mechanical characterization of the glass-ce-ramics with different （CaO ＋ MgO）/（SiO2 ＋ Al2O3） content ratios were studied. While the basicity decreases from 1.2 to 0.9 cm^-3, the bridge oxygen content increases from 1.18 ~ 10^21 to 1.34 ~ 10^21 cm^-3. According to the deconvolution of Raman spectra, the relative abundance of the stretching of Si-Onb bond （Q^n units） can be obtained. The increase in the Q^3 units dominates the polymerization in the process of decreasing basicity. This change in bonding is demonstrated to lead to polymerization of the glass network and the increase in crystallization activation energy from 336.0 to 360.7 kJ·mol^-l. The results demonstrate that the production of the glass-ceramics from industrial steel slag, fly ash and coal fly ash is cost-effective and offers advantages over other production methods.

Characterization of landfilled stainless steel slags in view of metal recovery

The slag samples taken from landfill, which originated from different metallurgical processes, have been characterized in this study. The slags were categor- ized as electric arc furnace （EAF） slag, argon oxygen decarburization/metal refining process slag and vacuum oxygen decarburization slag based on chromium content and basicity. EAF slags have higher potential in metal recovery than the other two slags due to its higher iron and chromium contents. The size of the iron-chromium-nickel alloy particles varies from a few ~tm up to several cm. The recoveries of large metal particles and metal-spinel aggregates have potential to make the metal recovery from landfilled slags economically viable.

Mechanism and Prevention of Disintegration of AOD Stainless Steel Slag

During the cooling process of AOD（argon-oxygen decarburization）stainless steel slag,the serious disintegrating problem happened,which will cause serious environmental pollution.The disintegrating mechanism of the AOD slag was analyzed in detail,and experimental research on prevention of disintegrating of AOD stainless steel slag was developed by adjusting the basicity of the slag and adding the quartz sand and borax.The disintegrating problem during the cooling process of AOD stainless steel slag is caused by the 2CaO·SiO2phase transformation fromα＇-C2S toγ-C2S.By means of adjusting the basicity of the AOD stainless steel slag from 2to 1.5by adding quartz sand,disintegrating of slag was prevented.But the adding amount must arrive at 15% which increases the difficulty of industrialization.Disintegration of AOD stainless steel slag can be effectively controlled by adding borax,and the adding amount is only 0.5%-0.8%.This method can be easily industrialized.

Beneficial use of stainless steel EAF slag as composite cement admixture and its heavy metals leaching risk analysis

This study analyzes the feasibility of using stainless steel electric arc furnace （EAF） slag as composite cement admixture and the risk of leaching-out of heavy metals. The results show that the stainless steel EAF slag, mainly made up of Ca2 SiO4, Ca3 Mg （ SiO4 ） 2, some Cr-containing minerals and in small particle size, is easily ground and has cementitious activity. EAF slag, when used as cement admixture, can be added with a maximum percentage of 32%. It can meet the strength requirements of the standard P · C 32.5 cement. When the mixing percentage is decreased to 25 % , the strength of the cement can be increased to that of P · C 42.5 cement. Other main quality indexes of composite cement, such as the setting time and stability, also satisfy standard requirements. The results also show that most of the heavy metals in the stainless steel EAF slag exist in a stable speciation. The concentration of heavy metals that leach out from the stainless steel EAF slag and the composite cement products is far lower than the standard limit of hazardous wastes. The main heavy metal, chromium, exists as less hazardous trivalent chromium. Therefore, the risk of heavy metals leaching out from the stainless steel EAF slag is low. The internal exposure index （IRa） and the external exposure index （Iγ） of the stainless steel EAF slag are both lower than 1.0, satisfying the standard requirements of the state for the radionuclides of building materials. Therefore, stainless steel EAF slag can be safely used as admixture to produce composite cement.

Slag foaming experiments in EAF for stainless steel production

The foaming slag practice can effectively solve the problems existing in EAF smelting of stainless steel, such as high electrical consumption ,high refractory consumption and long tap to tap time. In this paper, theoretical analyses were made on the technical difficulties and development feasibility of the technology. Slag foaming experiments were performed in a 10t EAF where crude stainless steel with a Cr content of 13% - 15% and a carbon content of 1.5% - 2.5% was smelted and special foaming pellets were added to release additional gas for better foaming. Good foaming slag was observed with the electric arc fully covered by the foam when the content of Cr2O3 is between 7% - 12%. The industrial scale experiments were performed in a 110 t EAF by the use of the same foaming pellets. Compared with the traditional operation, these experiments resulted in better foaming effects.

Oxidation of Alloying Elements during ESR of Stainless Steel

The oxidation of alloying elements during the ESR of stainless steel has been studied. The model previously developed by WEI and Mitchell for the chemical reactions and mass transfer processes during ESR was applied to the remelting of the high Cr steel 1Cr18Ni9(Ti).The laboratory data for the unsteady state A.C.ESR were analyzed and dealt with by the model.When the remelting process reached a steady state,an oxidant(Fe_2O_3 powder)or a deoxidant(Ca-Si powder or metallic Ca)was added to the slag bath.The results showed that this model is applicable to the remelting of stainless steel rather precisely, and it is expected that the model may offer a reliable basis for the control of composition during practical ESR of high alloy steel. Also,the oxidation of Cr in the steel must be noticed when its content is high;but it is entirely possible to adjust the Cr content of ingot within a considerable range,using a special technique by means of the slag-metal reactions during the remelting.

TiO_(2)和碱度对CaO-MgO-Al_(2)O_(3)-SiO_(2)-Cr_(2)O_(3)-Fe_(2)O_(3)-TiO_(2)渣系黏度和结构及氧化铬溶解度的影响

为了更多地利用不锈钢渣制备微晶玻璃来固化渣中的Cr,本文系统研究了不同TiO_(2)和碱度对CaO-MgO-Al_(2)O_(3)-SiO_(2)-Cr_(2)O_(3)-Fe_(2)O_(3)-TiO_(2)渣系中Cr_(2)O_(3)的溶解度和渣系黏熔特性的影响。利用熔体物性综合测试仪、XRD和拉曼光谱分析仪探明在不同TiO_(2)含量(4%~10%)及不同碱度(C/S=0.5、0.75、1)下,渣系黏度、物相组成和结构的变化规律。结果表明,随着TiO_(2)含量和碱度的增加,Cr_(2)O_(3)在渣样中的溶解度增加,黏流活化能下降,渣系黏度也随之降低。与增加TiO_(2)相比,增加碱度更能有效降低渣系黏度。TiO_(2)含量和碱度的增加使渣中Q^(0)和Q^(1)结构单元数量增加及Q^(3)减少,简化了硅酸盐网络结构单元,降低了渣系黏度。同时,也阻碍了含铬尖晶石的结晶,增加了Cr_(2)O_(3)在渣样中的溶解度。

022Cr18Ti不锈钢酸洗板表面起皮缺陷原因分析

022Cr18Ti不锈钢热轧钢带在酸洗过程中发现表面存在长条状起皮缺陷,该类缺陷对后续使用存在较大的影响。对起皮缺陷进行了检测分析,确定表面起皮缺陷为铸坯皮下夹渣导致。研究并制定了相应的改进措施,有效解决了022Cr18Ti钢带表面的起皮问题。

连续光纤激光切割金属薄壁材料工艺研究

随着工业领域金属薄壁构件设计的多样化,在高速激光切割的同时,对切口形貌质量也提出了更高的要求。本研究采用连续光纤激光器对0.2 mm厚度304不锈钢薄板进行切割实验,研究了毛刺和熔渣飞溅区产生的机理,重点讨论了加工工艺参数中的激光功率、切割速度、离焦量对毛刺堆积量和熔渣飞溅区宽度的影响关系,通过实验分析获得了最佳加工参数组合。研究结果表明,毛刺厚度随着激光功率、离焦量的增大而增加,随着切割速度的增大先降低后增加。熔渣飞溅区宽度随着激光功率的增大而增加,随着切割速度的增大而降低,随着离焦量的增大出现小范围波动。根据加工结果分析,当激光功率为125 W,切割速度为10 m/min,辅助气体压强为1.2 MPa,离焦量为-0.3~-0.5 mm,可以获得0.2 mm厚304不锈钢薄板较好的加工效果。

利用不锈钢渣制备微晶玻璃的研究进展

工业的快速发展导致固体废弃物逐年增加,由其带来的环境与资源问题不容忽视。利用工业固体废弃物制备微晶玻璃材料是固废资源化利用的重要途径之一,同时,该方法还可实现有害重金属元素的固化,减少环境危害。本文基于不锈钢渣的来源与特性,对比分析了不锈钢渣无害化处理的常见方法。针对不锈钢渣的无害化处理和资源化利用问题,重点综述了利用不锈钢渣制备微晶玻璃过程中主要成分对材料结构与性能的影响;另外,基于微晶玻璃对重金属元素的固化研究现状,重点讨论了微晶玻璃对不锈钢渣中Cr、Ni、Mn重金属元素的固化;最后对不锈钢渣无害化处理与资源化利用的未来研究方向进行了展望。

304不锈钢氩氧脱碳精炼过程中炉渣成分预测模型

针对304不锈钢氩氧脱碳(Argon-Oxygen Decarburization,AOD)精炼过程中存在炉渣成分难以测量等问题,本研究综合考虑了顶枪吹氧、供气比例变化、物料熔化速度以及初始渣量对渣-钢反应和精炼炉渣成分的影响,建立了炉渣成分预测模型,并用于计算精炼过程中的炉渣和钢液成分变化。此模型计算的渣成分与钢液硫含量与实测值吻合较好,AOD精炼终点渣中SiO_(2)含量平均偏差为1.434%,CaO含量平均偏差为1.848%,Cr_(2)O_(3)含量平均偏差为0.080%,MnO含量平均偏差为0.016%,钢液终点S含量平均偏差为0.002%。

碳酸化-水化耦合养护对不锈钢渣净浆力学性能和Cr离子溶出的影响

在CO_(2)浓度为99%,压力为0.2 MPa条件下,对钢渣复合胶凝材料进行碳酸化-水化耦合养护,调节碳酸化-水化耦合机制和碳酸化时间,分析硬化浆体的抗压强度、固碳量、矿物组成、微观形貌以及Cr离子溶出规律。结果表明钢渣/水泥试块标准养护3 d后进行碳酸化养护,3 d和28 d强度均达到最高。水化养护3d后进行碳酸化养护1 h、2 h、6 h,可使3 d的抗压强度提升16.3%、26.5%、50.2%,后期水化强度持续增长,28 d强度分别提高17.6%、27.7%、22.8%且安定性良好。水化养护28 d后进行碳酸化的试块固碳量最高,这是因为水化养护3 d后进行碳化,参与碳化反应的主要是C2S、C3S等,水化养护28 d后进行碳化,参与碳酸化反应的主要是C-S-H凝胶、Ca(OH)2,及未反应的C2S、C3S等。C-S-H凝胶和Ca(OH)2碳化活性较高,固碳能力强,但碳化产物强度较低。不同的碳酸化-水化耦合机制对Cr离子的固化作用也有显著的影响,水化养护3 d后进行碳酸化处理的固化效果最好,碳酸化养护6 h的试块,Cr离子溶出降低58.2%。

不锈钢冶金废渣制备超细掺合料配比研究

在节能减排和绿色发展的背景下,大量堆放的冶金固废对环境污染的问题亟待解决。针对不锈钢生产过程中排放的工业固废—镍铁渣与不锈钢尾渣,复掺粉煤灰、脱硫石膏,以7d活性和28d活性为性能指标,基于力学性能进行配比优化研究。结果表明:不锈钢尾渣和镍铁渣的掺入比例对于超细掺合料的活性影响最大,其次是粉煤灰的掺入量,脱硫石膏的掺入量对于活性的影响相对较小。比表面积超过600cm^(2)/g以后继续粉磨对活性提升不明显。综合考虑制备超细固废掺合料的配比为镍铁渣:不锈钢尾渣=8∶2,粉煤灰掺量为20%,SO_(3)的含量控制在3.0%,比表面积为600cm^(2)/g,此时超细掺合料的28d活性最高,7d活性80%,28d活性达91%。

三元地质聚合物力学性能和微观结构研究

使用粉煤灰、矿粉和不锈钢渣粉制备三元地质聚合物,开展了原料配比、碱激发剂含量以及水玻璃模数对地质聚合物力学性能的影响,并利用SEM、EDS和XRD对试样进行了微观结构和物相成分分析。结果表明:在粉煤灰基础上,矿粉和不锈钢渣粉的添加降低了惰性晶体峰的强度,提高了试样的Si/Al,宏观表现为力学性能提高,当粉煤灰、矿粉和不锈钢渣粉占比为80%、60%、40%时,试样28 d抗压强度达到70.1 MPa;三元地质聚合物的抗压强度随着碱激发剂含量和模数的增加先提高后降低,同时抗压强度的提高会导致抗折强度降低试样变脆,且易出现收缩裂纹;与水泥相比,三元地质聚合物晶相主要为原料中未反应的惰性物质以及新生成的钠沸石和钙沸石,非晶相主要为C-S-H和N(C)-A-S-H共存产物。

1Cr13不锈钢连铸保护渣成分设计

在生产1Cr13不锈钢的过程中,铸坯出现了严重的纵裂漏钢及横向凹陷。利用FactSage8.2热力学软件计算三元以及四元相图对保护渣成分进行设计,同时,计算1Cr13不锈钢的凝固特性,由于该钢属于包晶钢,在凝固过程中会产生急剧的体积收缩,从而在坯壳薄弱处产生纵裂。为了避免初生坯壳不均匀引起的凹陷和纵裂,应适当提高保护渣碱度、改善保护渣结晶性能,并提升保护渣控制传热能力。新型保护渣碱度为1.5,渣成分为w[MgO]6%,w[Li_(2)O]2%,w[Al_(2)O_(3)]16%,w[Na_(2)O]8%,w[B_(2)O_(3)]3%,w[CaF_(2)]10%。1Cr13不锈钢原渣熔点为1155℃,定温黏度为0.442 Pa·s、转折温度1140℃,新型保护渣熔点为1120℃,黏度为0.304 Pa·s,转折温度为1171℃,结晶温度为1270℃。实际生产后,铸坯表面质量明显改善。